Dianionic amidinates at silicon and germanium centers: Four-, six- and eight-membered rings

Segmueller T, Schlueter PA, Drees M, Schier A, Nogai S, Mitzel NW, Strassner T, Karsch HH (2007)
JOURNAL OF ORGANOMETALLIC CHEMISTRY 692(13): 2789-2799.

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Abstract
At variance to an earlier finding, the reaction of Me2SiCl2 with Li[(Me)N-C(Ph)-NH] (1a), in the presence of a base, gives a six-membered ring molecule mu-[(Ph)(MeN)C-N][-SiMe2-N-C(Ph) N(Ph)-SiMe2-] (s3a), whereas with Li[(PrN)-Pr-i-C(Ph)-NH] (1b), a four-mernbered ring molecule mu-[(PrN)-Pr-i(Ph)C-N](2)(SiMe2)(2) (s4b) was formed. In contrast, with Li[(BuN)-Bu-t-C(Ph)-NH] (1c), no such reaction occurred. Obviously, a delicate influence of steric effects has to be taken into account. In fact, the latter amidinate reacts with GeCl2 to form an eight-membered ring molecule [(BuN)-Bu-t-C(Ph)-N-Ge](4) (5c) without adding an additional base. The compounds are fully characterized and their structures determined by X-ray diffraction. DFT calculations confirm the dependence on steric influences. The relative energies of ground and transition states give a rationalization the ease of transformations of the various rings via pathways with penta- and hexacoordinate silicon centers, which in turn relates to the experimental results on penta- and hexacoordinate silicon amidinates and their fluctional behavior in solution. (c) 2007 Elsevier B.V. All rights reserved.
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Segmueller T, Schlueter PA, Drees M, et al. Dianionic amidinates at silicon and germanium centers: Four-, six- and eight-membered rings. JOURNAL OF ORGANOMETALLIC CHEMISTRY. 2007;692(13):2789-2799.
Segmueller, T., Schlueter, P. A., Drees, M., Schier, A., Nogai, S., Mitzel, N. W., Strassner, T., et al. (2007). Dianionic amidinates at silicon and germanium centers: Four-, six- and eight-membered rings. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 692(13), 2789-2799. doi:10.1016/j.jorganchem.2007.02.032
Segmueller, T., Schlueter, P. A., Drees, M., Schier, A., Nogai, S., Mitzel, N. W., Strassner, T., and Karsch, H. H. (2007). Dianionic amidinates at silicon and germanium centers: Four-, six- and eight-membered rings. JOURNAL OF ORGANOMETALLIC CHEMISTRY 692, 2789-2799.
Segmueller, T., et al., 2007. Dianionic amidinates at silicon and germanium centers: Four-, six- and eight-membered rings. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 692(13), p 2789-2799.
T. Segmueller, et al., “Dianionic amidinates at silicon and germanium centers: Four-, six- and eight-membered rings”, JOURNAL OF ORGANOMETALLIC CHEMISTRY, vol. 692, 2007, pp. 2789-2799.
Segmueller, T., Schlueter, P.A., Drees, M., Schier, A., Nogai, S., Mitzel, N.W., Strassner, T., Karsch, H.H.: Dianionic amidinates at silicon and germanium centers: Four-, six- and eight-membered rings. JOURNAL OF ORGANOMETALLIC CHEMISTRY. 692, 2789-2799 (2007).
Segmueller, Thomas, Schlueter, Peter A., Drees, Markus, Schier, Annette, Nogai, Stefan, Mitzel, Norbert W., Strassner, Thomas, and Karsch, Hans H. “Dianionic amidinates at silicon and germanium centers: Four-, six- and eight-membered rings”. JOURNAL OF ORGANOMETALLIC CHEMISTRY 692.13 (2007): 2789-2799.
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